A subject of the invention is a composition for the oxidation dyeing of keratinous fibers, such as human keratinous fibers such as hair, comprising at least one oxidation base and at least one coupler chosen from N-(2-hydroxybenzene)carbamate and N-(2-hydroxybenzene)urea compounds of formula (I), their use as coupler for the oxidation dyeing of keratinous fibers, and the oxidation dyeing methods using them.
It is known to dye keratinous fibers, for example, human hair with dyeing compositions containing oxidation dye precursors, such as para-phenylenediamines, ortho-, and para-aminophenols, heterocyclic compounds such as diaminopyrazole derivatives, generally called oxidation bases. Oxidation dye precursors, i.e., oxidation bases, are colorless or weakly colored compounds which when combined with oxidizing products, can give rise, through a process of oxidative condensation, to colored or coloring compounds.
It is also known that it is possible to vary the shades obtained with these oxidation bases by combining them with couplers or color modifiers, the latter being chosen, for example, from aromatic meta-diamines, meta-aminophenols, meta-diphenols, noncationic naphthols or alternatively certain heterocyclic compounds such as indolic couplers.
The variety of molecules used in oxidation bases and couplers allows a rich palette of colors to be obtained.
The xe2x80x9cpermanentxe2x80x9d color obtained using these oxidation dyes should moreover satisfy at least one of a number of objectives. Thus, it should, for example, satisfy at least one of the following: be without drawbacks from the toxicological point of view, make it possible to obtain shades in the desired intensity and exhibit good resistance towards external agents (at least one of light, adverse weather conditions, washing, permanent waving, perspiration, and rubbing).
The dyes may also cover grey hair and may also be the least selective possible, that is to say, make it possible to obtain the smallest possible differences in color right along the same keratinous fiber, which may indeed be differently sensitized (i.e. damaged) between its tip and its root.
Oxidation dyeing compositions containing certain derivatives of N-(2-hydroxy-4-aminophenyl)acetamide as couplers have already been described, for example, in patent applications WO 98/52519, JP2521636, FR-A-1 596 879 and FR-A-2 233 984. However, such compositions are not always satisfactory based on the intensity of the colors which may be obtained.
However, the inventors have discovered, completely unexpectedly and surprisingly, that compounds of N-(2-hydroxybenzene)carbamate and N-(2-hydroxybenzene)urea compounds of formula (I) defined below are suitable as couplers for oxidation dyeing, and that they make it possible to obtain dyeing compositions leading to at least one of the following advantages: intense colors which are particularly chromatic and brilliant, colors which are not very selective, a broad palette of colors, and properties of resistance to the various treatments to which keratinous fibers may be subjected.
One embodiment of the invention is therefore a composition for oxidation dyeing keratinous fibers, for example, human keratinous fibers such as hair, comprising in a medium suitable for dyeing:
(a) at least one oxidation base; and
(b) at least one coupler chosen from compounds of formula (I) and acid addition salts thereof: 
in which:
R1 is chosen from a hydrogen atom, linear and branched, saturated and unsaturated (comprising, for example, at least one double bond and at least one triple bond) groups comprising from 1-15 carbon atoms, optionally substituted with at least one halogen atom, wherein at least one carbon atom is optionally replaced by a unit chosen from an oxygen atom, a nitrogen atom, a sulfur atom, and a SO2 group, and at least one branch of said branched groups optionally forms at least one 3- to 7-membered ring comprising at least one carbon atom, with the provisos that:
(i) said R1 does not comprise a group chosen from a peroxide group, a diazo group, a nitro group, and a nitroso group, and
(ii) said SO2 group is not directly linked to the nitrogen at the 7-position of formula (I);
X is chosen from groups OR5 and NR6R7, wherein
R5 is chosen from linear and branched, saturated and unsaturated (comprising, for example, at least one double bond and at least one triple bond) groups comprising from 1-20 carbon atoms, optionally substituted with at least one halogen atom, wherein at least one carbon atom is optionally replaced by a unit chosen from an oxygen atom, a nitrogen atom, a sulfur atom, and a SO2 group, and at least one branch of said branched groups optionally forms at least one 3- to 7-membered ring comprising at least one carbon atom, with the proviso that:
(i) said R5 does not comprise a group chosen from a peroxide group, a diazo group, a nitro group, and a nitroso group;
R6 and R7, which are identical or different, are each chosen from a hydrogen atom, linear and branched, saturated and unsaturated (comprising, for example, at least one double bond and at least one triple bond) groups comprising from 1-20 carbon atoms, optionally substituted with at least one halogen atom, wherein at least one carbon atom is optionally replaced by a unit chosen from an oxygen atom, a nitrogen atom, a sulfur atom, and a SO2 group, and at least one branch of said branched groups optionally forms at least one 3- to 7-membered ring comprising at least one carbon atom, with the proviso that:
(i) both said R6 and R7 do not comprise a group chosen from a peroxide group, a diazo group, a nitro group, and a nitroso group, and
said R6 and R7 optionally form a ring chosen from a saturated and an unsaturated ring comprising 5- to 7-members, wherein said members are each chosen from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a carbonyl group, and said members are optionally substituted with 1 or 2 groups R, wherein
R is chosen from linear, branched, saturated and unsaturated (comprising, for example, at least one double bond and at least one triple bond), C1-C6 alkyl groups, optionally substituted with at least one halogen atom, wherein at least one carbon atom is optionally replaced by a unit chosen from an oxygen atom, a nitrogen atom, a sulfur atom, and a SO2 group, and at least one branch of said branched C1-C6 alkyl group optionally forms at least one saturated or unsaturated 3- to 6-membered ring; with the proviso that:
(i) said R does not comprise a group chosen from a peroxide group, a diazo group, a nitro group, and a nitroso group;
wherein
said R1 and said R5 optionally form a ring chosen from a saturated and an unsaturated (comprising, for example, at least one double bond and at least one triple bond) ring comprising 5- to 7-members, wherein said members are each chosen from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a carbonyl group, and said members are optionally substituted with 1 or 2 groups R as defined above, with the proviso that:
(i) said R does not comprise a group chosen from a peroxide group, a diazo group, a nitro group, and a nitroso group; and
said R1 and said R6 optionally form a ring, chosen from a saturated and an unsaturated (comprising, for example, at least one double bond and at least one triple bond) ring comprising 5- to 7-members, wherein said members are each chosen from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a carbonyl group, and said members are optionally substituted with 1 or 2 groups R as defined above, with the proviso that:
(i) said R does not comprise a group chosen from a peroxide group, a diazo group, a nitro group, and a nitroso group;
R2, R3, and R4, which are identical or different, are each chosen from a hydrogen atom, a halogen atom, and linear and branched, saturated and unsaturated (comprising, for example, at least one double bond and at least one triple bond) groups comprising from 1-20 carbon atoms, optionally substituted with at least one halogen atom, wherein at least one carbon atom is optionally replaced by a unit chosen from an oxygen atom, a nitrogen atom, a sulfur atom, and a SO2 group, and at least one branch of said branched groups optionally form at least one 3- to 7-membered ring comprising at least one carbon atom, with the provisos that:
(i) said R2, R3 and R4 do not comprise a group chosen from a peroxide group, a diazo group, a nitro group, and a nitroso group;
(ii) said R4 is chosen from a group other than a hydroxyl group, a thio group, an amino group, and a substituted or unsubstituted sulphonylamino group; and
(iii) said R2, R3 and R4 are not directly linked to the benzene ring of formula (I) by a xe2x80x94NHxe2x80x94NHxe2x80x94;
wherein
said R1 and said R2 optionally form a saturated ring comprising 5- to 7-members, wherein said members are each chosen from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a carbonyl group, and said members are optionally substituted with 1 or 2 groups R as defined above, with the proviso that:
(i) said R does not comprise a group chosen from a peroxide group, a diazo group, a nitro group, and a nitroso group;
wherein
said R2 and said R5 optionally form a saturated ring comprising 5- to 7-members, wherein said members are each chosen from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a carbonyl group, and said members are optionally substituted with 1 or 2 groups R as defined above, with the provisos that:
(i) said R does not comprise a group chosen from a peroxide group, a diazo group, a nitro group, and a nitroso group; and
(ii) when said R2 and said R5 form a saturated ring comprising 5- to 7-members, said R5 optionally is a bond;
wherein
said R2 and said R6 optionally form a saturated ring comprising 5- to 7-members, wherein said members are each chosen from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a carbonyl group, and said members are optionally substituted with 1 or 2 groups R as defined above, with the provisos that:
(i) said R does not comprise a group chosen from a peroxide group, a diazo group, a nitro group, and a nitroso group; and
(ii) when said R2 and said R6 form a saturated ring comprising 5- to 7-members, said R6 optionally is a bond;
Y is chosen from:
a hydrogen atom;
a halogen atom;
a group chosen from xe2x80x94OR8, xe2x80x94SR8, and xe2x80x94NHxe2x80x94SO2R8, wherein
R8 is chosen from:
linear and branched C1-C8 alkyl groups, optionally substituted with at least one group chosen from a halogen atom, a hydroxyl group, C1-C4 alkoxy groups, an amino group, amino(C1-C4 alkyl) groups, a carboxyl group, and C1-C4 alkoxycarbonyl groups, wherein at least one branch of said branched C1-C8 alkyl groups optionally forms at least one 3- to 6-membered ring;
a phenyl group, optionally substituted with one or two groups chosen from C1-C4 alkyl groups, a trifluoromethyl group, a carboxyl group, C1-C4 alkoxycarbonyl groups, a halogen atom, a hydroxyl group, C1-C4 alkoxy groups, an amino group and amino(C1-C4 alkyl) groups; and
a benzyl group, optionally substituted with one or two oxy groups, with the proviso that:
(i) when R2 is a hydroxyl group, Y is not a xe2x80x94NHxe2x80x94SO2R8 group;
provided that:
(i) when said R2 and said R4 are hydrogen atoms, and when said R3 is chosen from substituted and unsubstituted C1-C4 alkyl groups, X is not a an xe2x80x94OR5 group, wherein R5 is chosen from substituted and unsubstituted C1-C4 alkyl groups;
(ii) when said R2 and said R4 are hydrogen atoms, and when said R3 is chosen form substituted and unsubstituted C1-C4 alkyl groups, X is not a NR6R7 group; and
(iii) when said R2, said R4, and said Y, are hydrogen atoms, and when said X is a NR6R7 group, wherein said R6 and R7 are hydrogen atoms, said R3 is not chosen from a fluorine atom, a chlorine atom and a bromine atom.
As indicated above, the colors obtained with the oxidation dyeing composition comprising a compound of formula (I) in accordance with the invention can be intense or brilliant and can contribute to a palette of highly chromatic colors. Such compositions may also exhibit properties of resistance towards the action of various external agents (at least one of light, adverse weather conditions, washing, permanent waving, perspiration, and rubbing).
In one embodiment of the invention, when either one or both of the following conditions are present: (1) when one or more carbon atoms of the radical(s) R1 to R7 are replaced by a substituent chosen from an oxygen atom, a nitrogen atom, a sulfur atom, and a SO2 group, and (2) when said radicals R1 to R7 are saturated (e.g., contain one or more double bonds and/or one or more triple bonds); it is possible, by way of example, to make the following conversions: 
In one embodiment, R1 is chosen from a hydrogen atom, and a group chosen from A1, A2, A3, A4 and A5 as defined below, provided that when R1 is chosen from Groups A1, A2, A3, A4, and A5, R1 is optionally attached to the nitrogen at the 7-position by way of a group xe2x80x94(CO)xe2x80x94.
a Group A1, wherein said Group A1 is chosen from a hydroxyl group, a dimethylamino group, and linear and branched C1-C8 alkyl groups optionally unsaturated (optionally comprising one double bond, two double bonds, or one triple bond) and optionally substituted with at least one unit chosen from:
a group A2, A4, or A5 as defined below;
one or two groups, which may be identical or different, chosen from Nxe2x80x94(C1-C3)alkylamino, Nxe2x80x94(C1-C3)alkyl-Nxe2x80x94(C1-C3)alkylamino, (C1-C6)alkoxy, oxo, alkoxycarbonyl, acyloxy, amide, acylamino, ureyl, sulphoxy, sulphonyl, sulphonamido, sulphonylamino, bromo, cyano, amino, and carboxyl; and
at least one group chosen from a hydroxyl group, a fluoro group and a chloro group;
a Group A2, wherein said Group A2 is an aromatic group chosen from a phenyl group, and a naphthyl group, wherein said aromatic group is optionally substituted with one to three groups, which are identical or different, chosen from methyl, trifluoromethyl, ethyl, isopropyl, butyl, pentyl, fluoro, chloro, bromo, methoxy, trifluoromethoxy, ethoxy, propyloxy, acetyloxy, acetyl, amino, an oxy, and cyano;
a Group A3, wherein said Group A3 is a heteroaromatic group chosen from furanyl, thiophenyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, isoxazolyl, isothiazolyl, pyrazolyl, pyrazolotriazolyl, pyrazoloimidazolyl, pyrrolotriazolyl, pyrazolopyrimidyl, pyrazolopyridyl, pyridyl, pyrimidyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, indolyl, indolidinyl, isoindolyl, indazolyl, benzotriazolyl, quinolinyl, benzoimidazolyl and benzopyrimidyl, wherein said heteroaromatic group is optionally substituted with 1 to 3 groups chosen from linear and branched C1-C4 alkyl groups, a C1-C4 monohydroxyalkyl group, a C2-C4 polyhydroxyalkyl group, a carboxyl group, an alkoxycarbonyl group, an amido group, an amino group, a hydroxyl group, and a halogen atom.
a Group A4, wherein said Group A4 is chosen from a C3-C7 cycloalkyl group and a norbornyl group; wherein said C3-C7 cycloalkyl group and said norbornyl group further comprise at least one double bond and wherein said C3-C7 cycloalkyl group and said norbornyl group are optionally substituted with 1 or 2 units chosen from linear and branched C1-C4 alkyl groups, a C1-C4 monohydroxyalkyl group, a C2-C4 polyhydroxyalkyl group, a carboxyl group, an alkoxycarbonyl group, an amido group, an amino group, a hydroxyl group, an oxy group, and a halogen atom.
a Group A5, wherein said Group A5 is a heterocycle chosen from dihydrofuranyl, tetrahydrofuranyl, butyrolactonyl, dihydrothiophenyl, tetrahydrothiophenyl, tetrahydrothiophenonyl, iminothiolane, dihydropyrrolyl, pyrrolidinyl, pyrrolidinonyl, imidazolidinonyl, imidazolidinethionyl, oxazolidinyl, oxazolidinonyl, oxazolanethione, thiazolidinyl, isothiazolonyl, mercaptothiazolinyl, pyrazolidinonyl, iminothiolane, dioxolanyl, pentalactone, dioxanyl, dihydropyridinyl, piperidinyl, pentalactam, morpholinyl, pyrazoli(di)nyl, pyrimi(di)nyl, pyrazinyl, piperazinyl, and azepinyl.
In another embodiment, R1 is a chosen from:
a hydrogen atom;
a group chosen from methyl, ethyl, isopropyl, allyl, phenyl, benzyl, fluorobenzyl, difluorobenzyl, trifluorobenzyl, chlorobenzyl, bromobenzyl, methoxybenzyl, dimethoxybenzyl, (trifluoromethoxy)benzyl, 3,4-methylenedioxybenzyl, 6-chloropiperonyl, 4-methylthiobenzyl, 4-methylsulphonylbenzyl, 4-acetylaminobenzyl, 4-carboxybenzyl, 1-naphthomethyl and 2-naphthomethyl; and
a group chosen from 2-hydroxyethyl, 2-methoxyethyl and 2-ethoxyethyl.
In another embodiment, R1 is chosen from a hydrogen atom and a methyl group.
In one embodiment, R5 is chosen from Groups A1, A2, A3, A4, and A5, as defined above. In yet another embodiment of the invention, R5 is a group chosen from:
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, 1-methylvinyl, 2-methylvinyl, 2,2-dimethylvinyl, allyl, propargyl, chloromethyl, 2-chloroethyl, 2-hydroxyethyl, 2-methoxyethyl, 4-chlorobutyl, phenyl, 4-methylphenyl, 4-ethylphenyl, 4-(trifluoromethyl)phenyl, 4-hydroxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-acetoxyphenyl, 4-aminophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, naphth-1-yl, naphth-2-yl, and benzyl.
In another embodiment, when R1 and R5 form a ring, the ring is a group chosen from 2-oxazolidon-1-yl, 4-methyloxazolidon-1-yl, and 5,5-dimethyloxazoline-2,4-dion-1-yl.
In another embodiment, R5 is a group chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-hydroxyethyl, 2-methoxyethyl, allyl, phenyl, benzyl, cyclopentyl, and cyclohexyl.
In one embodiment of the invention, R6 and R7, which are identical or different, are each chosen from A1, A2, A3, A4, and A5, as defined above. In another embodiment, these substituents, R6 and R7, which are identical or different, are each chosen from:
a hydrogen atom, and
a group chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, cyclopentyl, cyclohexyl, allyl, propargyl, 2-chloroethyl, 2-hydroxyethyl, 2-methoxyethyl, 3-chloropropyl, 3-hydroxypropyl, 2,3-dihydroxypropyl, carboxymethyl, phenyl, fluorophenyl, (trifluoromethyl)phenyl, chlorophenyl, bromophenyl, methylphenyl, 4-acetylphenyl, methoxyphenyl, (trifluoromethoxy)phenyl, naphth-1-yl, benzyl, phenethyl and pyrid-3-yl.
In another embodiment, when R6 and R7 form a ring, said ring may be a group chosen from pyrrolidin-1-yl, 3-hydroxypyrrolidin-1-yl, 3,4-dihydroxypyrrolidin-1-yl, piperidin-1-yl, 3-hydroxypiperidin-1-yl, 4-hydroxypiperidin-1-yl, 4-morpholin-1-yl, piperazin-1-yl, 4-methylpiperazin-1-yl, and 4-(2-hydroxyethyl)piperazin-1-yl.
In still another embodiment, when R1 and R6 form a ring, the ring may be a group chosen from imidazolidin-2-on-1-yl and tetrahydropyrimidin-2-on-1-yl.
In one embodiment, R6 and R7, which are identical or different, are each chosen from a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an allyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, a 3-hydroxypropyl group, a 2,3-dihydroxypropyl group, a benzyl group, a cyclopentyl group, and cyclohexyl group.
In another embodiment, R2 and R3, which are identical or different, are each chosen from:
a hydrogen atom,
a halogen atom,
a hydroxyl group,
an amino group,
a group chosen from Group A1, Group A4, and Group A5, as defined above,
a group chosen from Group A1, Group A2, Group A3, Group A4 and Group A5, as defined above, wherein said groups are attached to the phenolic nucleus in formula (I) by way of a group chosen from an oxygen atom, and a group chosen from xe2x80x94NHxe2x80x94, xe2x80x94Nalkyl(C1-C3)xe2x80x94, xe2x80x94O(CO)xe2x80x94, xe2x80x94NH(CO)xe2x80x94, xe2x80x94Nalkyl(C1-C3)(CO)xe2x80x94, xe2x80x94NH[Cxe2x95x90NH]xe2x80x94, xe2x80x94NH(CO)NHxe2x80x94, xe2x80x94NH(CO)Nalkyl(C1-C3)xe2x80x94, xe2x80x94NH(CO)Oxe2x80x94, xe2x80x94NHSO2xe2x80x94, xe2x80x94NHSO2NHxe2x80x94 and xe2x80x94NHSO2Nalkyl(C1-C3)xe2x80x94.
In another embodiment, among these substituents, R2 is chosen from:
a hydrogen atom,
a chlorine atom,
a group chosen from methyl, hydroxymethyl, methoxymethyl, 2-hydroxyethyl, aminomethyl, methylaminomethyl, hydroxyl, methoxy, acetoxy, amino, methylamino and 2-hydroxyethylamino,
a group xe2x80x94NH(CO)R9, wherein in R9 is a moiety of a group (G1) chosen from:
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentylmethyl, 3-cyclopentylpropyl, cyclohexyl, 2-cyclohexylethyl, norborn-2-yl, vinyl, 1-methylvinyl, 2-methylvinyl, 2,2-dimethylvinyl, allyl, 3-butenyl, phenyl, methylphenyl, dimethylphenyl, 2,4,6-trimethylphenyl, 4-ethylphenyl, (trifluoromethyl)phenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, acetoxyphenyl, (trifluoromethoxy)phenyl, aminophenyl, 4-dimethylaminophenyl, fluorophenyl, difluorophenyl, fluoro(trifluoromethyl)phenyl, chlorophenyl, dichlorophenyl, bromophenyl, naphth-1-yl, naphth-2-yl, (2-methoxy)naphth-1-yl, benzyl, 4xe2x80x2-methoxybenzyl, 2xe2x80x2,5xe2x80x2-dimethoxybenzyl, 3xe2x80x2,4xe2x80x2-dimethoxybenzyl, 4xe2x80x2-fluorobenzyl, 4xe2x80x2-chlorobenzyl, phenethyl, 2-phenylvinyl, (1-naphthyl)methyl, (2-naphthyl)methyl, tetrahydrofuran-2-yl, furan-2-yl, 5-methyl-2-(trifluoromethyl)furan-3-yl, 2-methyl-5-phenylfuran-3-yl, thiophen-2-yl, (thiophen-2-yl)methyl, 3-chlorothiophen-2-yl, 2,5-dichlorothiophen-3-yl, benzothiophen-2-yl, 3-chlorobenzothiophen-2-yl, isoxazol-5-yl, 5-methylisoxazol-3-yl, 3,5-dimethylisoxazol-4-yl, 1,3-dimethylpyrazol-5-yl, 1-ethyl-3-methylpyrazol-5-yl, 1-tert-butyl-3-methylpyrazol-5-yl, 3-tert-butyl-1-methylpyrazol-5-yl, 4-bromo-1-ethyl-3-methylpyrazol-5-yl, indol-3-ylcarboxyl, pyridinyl, chloropyridinyl, dichloropyridinyl, 5-(bromo)pyridin-3-yl, piperazin-2-yl, quinoxal-2-yl, fluoromethyl, difluoromethyl, trifluoromethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl, 1,1,2,2,3,3,4,4-octafluorobutyl, nonafluorobutyl, chloromethyl, chloroethyl, 1,1-dimethyl-2-chloroethyl, 1,2-dichloroethyl, 1-chloropropyl, 3-chloropropyl, 4-chlorobutyl, hydroxymethyl, methoxymethyl, phenoxymethyl, (4-chlorophenoxy)methyl, benzyloxymethyl, acetoxymethyl, 1,2-dihydroxyethyl, 1-phenoxyethyl, 1-acetoxyethyl, 2-(2-carboxyethoxy)ethyl, 1-phenoxyethyl, 1-acetoxyethyl, methoxycarbonyl, ethoxycarbonyl, (methoxycarbonyl)methyl, 2-carboxyethyl, 2-(methoxycarbonyl)ethyl, 2-carboxycyclopropyl, 2-carboxycyclohexane, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, neopentoxy, hexyloxy, cyclopentyloxy, cyclohexyloxy, vinyloxy, allyloxy, propargyloxy, chloromethoxy, 1-chloroethoxy, 1-chloroethoxy, 2-methoxyethoxy, 4-chlorobutoxy, phenoxy, 4-methylphenoxy, 4-fluorophenoxy, 4-bromophenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, naphth-2-yloxy, benzyloxy, amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, cyclohexylamino, allylamino, 2-chloroethylamino, 3-chloropropylamino, carboxymethylamino, phenylamino, fluorophenylamino, (trifluoromethyl)phenylamino, chlorophenylamino, bromophenylamino, 4-acetylphenylamino, methoxyphenylamino, (trifluoromethoxy)phenylamino, naphth-1-ylamino, benzylamino, phenethylamino, pyridylamino, pyrid-3-ylamino, dimethylamino, 1-pyrrolidinyl and 4-morpholinyl radical,
a group xe2x80x94NHSO2R10, wherein R10 is a unit of a group (G2), chosen from:
methyl, trifluoromethyl, ethyl, 2-chloroethyl, propyl, 3-chloropropyl, isopropyl, butyl, thiophen-2-yl, hydroxyl, ethoxy and dimethylamino.
In one embodiment, when R1 and R2 form a ring together with the nitrogen atom at the 7-position of the compound of formula (I), wherein xe2x80x94R1R2xe2x80x94 may be xe2x80x94CH2CH2CH2xe2x80x94.
In another embodiment, when R2 and R5 form a ring, together with the nitrogen atom at the 7-position of the compound of formula (I), wherein xe2x80x94R2R5xe2x80x94 is chosen from xe2x80x94CH2xe2x80x94 and xe2x80x94C(CH3)2xe2x80x94.
In yet another embodiment of the invention, when R2 and R6 form a ring, together with the nitrogen atom at the 7-position of the compound of formula (I), wherein xe2x80x94R2R6xe2x80x94 is chosen from xe2x80x94CH2xe2x80x94 and xe2x80x94C(CH3)2xe2x80x94.
In another embodiment of the invention, R2 is chosen from:
a hydrogen atom,
a group chosen from methyl, hydroxymethyl, aminomethyl, hydroxyl, methoxy, amino, and methylamino,
a group chosen from methanesulphonylamino, ethanesulphonylamino, and dimethylaminosulphonylamino, and
a group xe2x80x94NH(CO)R11 wherein R11 is a radical of a group (G3) chosen from:
methyl, ethyl, propyl, allyl, phenyl, tetrahydrofuran-2-yl, furan-2-yl, thiophen-2-yl, pyridinyl, piperazin-2-yl, fluoromethyl, chloromethyl, 2-chloroethyl, methoxymethyl, acetoxymethyl, 1,2-dihydroxyethyl, methoxycarbonyl, 2-carboxyethyl, methoxy, ethoxy, propoxy, allyloxy, 2-chloroethoxy, 2-methoxyethoxy, amino, ethylamino, allylamino, 2-chloroethylamino, pyridylamino, dimethylamino, 1-pyrrolidinyl and 4-morpholinyl.
Among these substituents, in one embodiment of the invention, R3 is chosen from:
a hydrogen atom,
a chlorine atom,
a group chosen from methyl, ethyl, hydroxymethyl, 2-hydroxyethyl, methoxymethyl, aminomethyl, methylaminomethyl, hydroxyl, methoxy, acetoxy, amino, methylamino, 2-hydroxyethylamino, N-piperidino and N-morpholino,
a group xe2x80x94NH(CO)R12, wherein R12 is a unit of said group (G1), as defined above, and
a group xe2x80x94NHSO2R13, wherein R13 is a unit of said group (G2), as defined above.
In another embodiment, R3 is chosen from
a hydrogen atom,
a chlorine atom,
a group chosen from methyl, hydroxymethyl, aminomethyl, hydroxyl, methoxy, amino and methylamino,
a group chosen from methanesulphonylamino, ethanesulphonylamino, and dimethylaminosulphonylamino, and
a group xe2x80x94NH(CO)R14 wherein R14 is a unit of said group (G3), as defined above.
In one embodiment, R4 is chosen from:
a hydrogen atom,
a halogen atom,
a group chosen from A1, A4 and A5, as defined above,
a group chosen from A1, A2, A3, A4 and A5, as defined above, wherein said groups are attached to the phenolic nucleus in formula (I) by way of a group chosen from an oxygen atom, a sulfur atom, and a group chosen from xe2x80x94NHxe2x80x94, xe2x80x94Nalkyl(C1-C3)xe2x80x94, xe2x80x94O(CO)xe2x80x94, xe2x80x94NH(CO)xe2x80x94, xe2x80x94Nalkyl(C1-C3)(CO)xe2x80x94, xe2x80x94NH[Cxe2x95x90NH]xe2x80x94, xe2x80x94NH(CO)NHxe2x80x94, xe2x80x94NH(CO)Nalkyl(C1-C3)xe2x80x94, and xe2x80x94NH(CO)Oxe2x80x94.
In another embodiment, among these substituents, R4 is chosen from:
an atom chosen from hydrogen, chlorine, fluorine, and bromine,
a group chosen from methyl, trifluoromethyl, allyl, hydroxymethyl, methoxymethyl, 2-hydroxyethyl, aminomethyl, methylaminomethyl, methoxy, acetoxy and methylamino, and
a group xe2x80x94NH(CO)R15 wherein R15 is a unit of said group (G1), as defined above.
in yet another embodiment, R4 is chosen from:
an atom chosen from hydrogen, chlorine, and fluorine,
a group chosen from methyl, hydroxymethyl, aminomethyl, methoxy and methylamino,
a group xe2x80x94NH(CO)R16 wherein R16 is a unit of said group (G3), as defined above.
In one embodiment, Y is chosen from:
an atom chosen from hydrogen, chlorine, fluorine, and bromine,
a group chosen from methoxy, ethoxy, propoxy, benzyloxy, phenoxy, xe2x80x94OCH2CH2OCH3, xe2x80x94OCH2OCH2OCH3, xe2x80x94OCH2CH2N(CH3)2, xe2x80x94OCH2(CO)OH, xe2x80x94OCH2(CO)OCH3, xe2x80x94OCH2(CO)OC2H5, xe2x80x94SCH2CH2CO2H, and xe2x80x94NHSO2CH3,
with the proviso that when R2 is a hydroxyl group, Y is other than a xe2x80x94NHSO2CH3 group.
In another embodiment, Y is chosen from a hydrogen atom, a chlorine atom, a methoxy group, a xe2x80x94OCH2(CO)OH group, and a xe2x80x94OCH2(CO)OCH3 group.
In one embodiment, at least one coupler of formula (I), is chosen from the Groups (i), (ii), (iii), and (iv) in which:
Group (i) is said at least one coupler of formula (I), wherein:
R1 is a hydrogen atom,
X is a group chosen from methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, isobutyloxy, 2-hydroxyethoxy, 2-methoxyethoxy, allyloxy, amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, 2-hydroxyethylamino, 2-methoxyethylamino, 3-hydroxypropylamino, 2,3-dihydroxypropylamino, allylamino, dimethylamino, diethylamino, di(2-hydroxyethyl)amino, pyrrolidin-1-yl, 3-hydroxypyrrolidin-1-yl, and 3,4-dihydroxypyrrolidin-1-yl,
R2 is chosen from:
a group chosen from hydroxyl, amino, methylamino, 2-hydroxyethylamino and diethylamino,
a group xe2x80x94NH(CO)R17, wherein R17 is a unit of group (G4), said moiety is chosen from a methyl group, a methoxymethyl group, a 2-carboxyethyl group, a methoxy group, an amino group, an ethylamino group, a 1-pyrrolidinyl group, a methanesulphonylamino group, an ethanesulphonylamino group, and a dimethylaminosulphonylamino group,
R3 is chosen from a hydrogen atom, a chlorine atom, and a methyl group,
R4 is chosen from a hydrogen atom, a chlorine atom, a fluorine atom, and a methyl group, and
Y is chosen from a hydrogen atom, a chlorine atom, a methoxy group, and a xe2x80x94OCH2(CO)OCH3 group,
Group (ii) is said at least one coupler of formula (I), wherein:
R1 is a hydrogen atom,
X is a group chosen from methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, isobutyloxy, 2-hydroxyethoxy, 2-methoxyethoxy, allyloxy, amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, 2-hydroxyethylamino, 2-methoxyethylamino, 3-hydroxypropylamino, 2,3-dihydroxypropylamino, allylamino, dimethylamino, diethylamino, di(2-hydroxyethyl)amino, pyrrolidin-1-yl, 3-hydroxypyrrolidin-1-yl, and 3,4-dihydroxypyrrolidin-1-yl,
R2 is chosen from a hydrogen atom and a methyl group;
R3 is chosen from:
a group chosen from hydroxyl, amino, methylamino, 2-hydroxyethylamino, diethylamino, methanesulphonylamino, ethanesulphonylamino and dimethylaminosulphonylamino; and
a group xe2x80x94NH(CO)R18, wherein R18 is a unit of group (G4), said moiety is chosen from a methyl group, a methoxymethyl group, a 2-carboxyethyl group, a methoxy group, an amino group, an ethylamino group, a 1-pyrrolidinyl group, a methanesulphonylamino group, an ethanesulphonylamino group, and a dimethylaminosulphonylamino group;
R4 is chosen from a hydrogen atom, a chlorine atom, a fluorine atom, and a methyl group; and
Y is a moiety chosen from a hydrogen atom, a chlorine atom, a methoxy group, and a xe2x80x94OCH2(CO)OCH3 group;
Group (iii) is said at least one coupler of formula (I) wherein:
R1 is a hydrogen atom;
X is a group chosen from methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, isobutyloxy, 2-hydroxyethoxy, 2-methoxyethoxy, allyloxy, amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, 2-hydroxyethylamino, 2-methoxyethylamino, 3-hydroxypropylamino, 2,3-dihydroxypropylamino, allylamino, dimethylamino, diethylamino, di(2-hydroxyethyl)amino, pyrrolidin-1-yl, 3-hydroxypyrrolidin-1-yl, and 3,4-dihydroxypyrrolidin-1-yl;
R2 is chosen from a hydrogen atom, and a methyl group;
R3 is chosen from a hydrogen atom, a chlorine atom, a methyl group, a methoxy group and a methylamino group;
R4 represents a group xe2x80x94NH(CO)R19, wherein R19 is a unit of group (G4), said moiety is chosen from a methyl group, a methoxymethyl group, a 2-carboxyethyl group, a methoxy group, an amino group, an ethylamino group, a 1-pyrrolidinyl group; a methanesulphonylamino group, an ethanesulphonylamino group, and a dimethylaminosulphonylamino group; and
Y is chosen from a hydrogen atom, a chlorine atom, a methoxy group, and a xe2x80x94OCH2(CO)OCH3 group; and
Group (iv) is said at least one coupler of formula (I) wherein:
R1 is a hydrogen atom;
X is a group chosen from methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, isobutyloxy, 2-hydroxyethoxy, 2-methoxyethoxy, allyloxy, amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, 2-hydroxyethylamino, 2-methoxyethylamino, 3-hydroxypropylamino, 2,3-dihydroxypropylamino, allylamino, dimethylamino, diethylamino, di(2-hydroxyethyl)amino, pyrrolidin-1-yl, 3-hydroxypyrrolidin-1-yl, and 3,4-dihydroxypyrrolidin-1-yl;
R2 is chosen from a hydrogen atom and a methyl group;
R3 is chosen from a hydrogen atom, a methyl group and an ethyl group;
R4 is chosen from a hydrogen atom, a chlorine atom, and a fluorine atom; and
Y is chosen from a hydrogen atom, a chlorine atom and a xe2x80x94OCH2(CO)OCH3 group.
In one embodiment of the invention, the at least one coupler of formula (I) is chosen from:
(2-Hydroxyphenyl)carbamic acid methyl ester,
(2-Hydroxyphenyl)carbamic acid ethyl ester,
(2-Hydroxyphenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxyphenyl)carbamic acid isopropyl ester,
1-(2-Hydroxyphenyl)urea,
3-(2-Hydroxyphenyl)-1-methylurea,
3-(2-Hydroxyphenyl)-1-ethylurea,
3-(2-Hydroxyphenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxyphenyl)-1-isopropylurea,
3-(2-Hydroxyphenyl)-1,1-dimethylurea,
3-(2-Hydroxyphenyl)-1,1-diethylurea,
3-(2-Hydroxyphenyl)-1,1-di(2-hydroxyethyl)urea,
(2-Hydroxy-5-chlorophenyl)carbamic acid methyl ester,
(2-Hydroxy-5-chlorophenyl)carbamic acid ethyl ester,
(2-Hydroxy-5-chlorophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-5-chlorophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-5-chlorophenyl)urea,
3-(2-Hydroxy-5-chlorophenyl)-1-methylurea,
3-(2-Hydroxy-5-chlorophenyl)-1-ethylurea,
3-(2-Hydroxy-5-chlorophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-5-chlorophenyl)-1-isopropylurea,
3-(2-Hydroxy-5-chlorophenyl)-1,1-dimethylurea,
3-(2-Hydroxy-5-chlorophenyl)-1,1-diethylurea,
3-(2-Hydroxy-5-chlorophenyl)-1,1-di(2-hydroxyethyl)urea,
(2-Hydroxy-5-methoxyphenyl)carbamic acid methyl ester,
(2-Hydroxy-5-methoxyphenyl)carbamic acid ethyl ester,
(2-Hydroxy-5-methoxyphenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-5-methoxyphenyl)carbamic acid isopropyl ester,
3-(2-Hydroxy-5-methoxyphenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-5-methoxyphenyl)-1,1-di(2-hydroxyethyl)urea,
(2-Hydroxy-6-aminophenyl)carbamic acid methyl ester,
(2-Hydroxy-6-aminophenyl)carbamic acid ethyl ester,
(2-Hydroxy-6-aminophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-6-aminophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-6-aminophenyl)urea,
3-(2-Hydroxy-6-aminophenyl)-1-methylurea,
3-(2-Hydroxy-6-aminophenyl)-1-ethylurea,
3-(2-Hydroxy-6-aminophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-6-aminophenyl)-1-isopropylurea,
3-(2-Hydroxy-6-aminophenyl)-1,1-dimethylurea,
3-(2-Hydroxy-6-aminophenyl)-1,1-diethylurea,
3-(2-Hydroxy-6-aminophenyl)-1,1-di(2-hydroxyethyl)urea,
(2-Hydroxy-4-aminophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-aminophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-aminophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-aminophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-aminophenyl)urea,
3-(2-Hydroxy-4-aminophenyl)-1-methylurea,
3-(2-Hydroxy-4-aminophenyl)-1-ethylurea,
3-(2-Hydroxy-4-aminophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-aminophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-aminophenyl)-1,1-dimethylurea,
3-(2-Hydroxy-4-aminophenyl)-1,1-diethylurea,
3-(2-Hydroxy-4-aminophenyl)-1,1-di(2-hydroxyethyl)urea,
Pyrrolidine-1-carboxylic acid (4-amino-2-hydroxyphenyl)amide,
3-Hydroxypyrrolidine-1-carboxylic acid (4-amino-2-hydroxyphenyl)amide,
(2-Hydroxy-4-methylaminophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-methylaminophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-methylaminophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-methylaminophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-methylaminophenyl)urea,
3-(2-Hydroxy-4-methylaminophenyl)-1-methylurea,
3-(2-Hydroxy-4-methylaminophenyl)-1-ethylurea,
3-(2-Hydroxy-4-methylaminophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-methylaminophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-methylaminophenyl)-1,1-dimethylurea,
3-(2-Hydroxy-4-methylaminophenyl)-1,1-diethylurea,
3-(2-Hydroxy-4-methylaminophenyl)-1,1-di(2-hydroxyethyl)urea,
(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)urea,
3-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)-1-methylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)-1-ethylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)-1,1-dimethylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)-1,1-diethylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)-1,1-di(2-hydroxyethyl)urea,
(2-Hydroxy-4-amino-5-chlorophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-amino-5-chlorophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-amino-5-chlorophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-amino-5-chlorophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-amino-5-chlorophenyl)urea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1-methylurea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1-ethylurea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1,1-dimethylurea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1,1-diethylurea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1,1-di(2-hydroxyethyl)urea,
(2-Hydroxy-4-methylamino-5-chlorophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-methylamino-5-chlorophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-methylamino-5-chlorophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-methylamino-5-chlorophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-methylamino-5-chlorophenyl)urea,
3-(2-Hydroxy-4-methylamino-5-chlorophenyl)-1-methylurea,
3-(2-Hydroxy-4-methylamino-5-chlorophenyl)-1-ethylurea,
3-(2-Hydroxy-4-methylamino-5-chlorophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-methylamino-5-chlorophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-methylamino-5-chlorophenyl)-1,1-dimethylurea,
3-(2-Hydroxy-4-methylamino-5-chlorophenyl)-1,1-diethylurea,
3-(2-Hydroxy-4-methylamino-5-chlorophenyl)-1,1-di(2-hydroxyethyl)urea,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)carbamic acid isopropyl ester,
1(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)urea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)-1-methylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)-1-ethylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)-1,1-dimethylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)-1,1-diethylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)-1,1-di(2-hydroxyethyl)urea,
(2-Hydroxy-4-amino-5-methoxyphenyl)carbamic acid methyl ester,
(2-Hydroxy-4-amino-5-methoxyphenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-amino-5-methoxyphenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-amino-5-methoxyphenyl)carbamic acid isopropyl ester,
3-(2-Hydroxy-4-amino-5-methoxyphenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-amino-5-methoxyphenyl)-1,1-di(2-hydroxyethyl)urea,
(2-Hydroxy-4-methylamino-5-methoxyphenyl)carbamic acid methyl ester,
(2-Hydroxy-4-methylamino-5-methoxyphenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-methylamino-5-methoxyphenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-methylamino-5-methoxyphenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-methylamino-5-methoxyphenyl)urea,
3-(2-Hydroxy-4-methylamino-5-methoxyphenyl)-1-methylurea,
3-(2-Hydroxy-4-methylamino-5-methoxyphenyl)-1-ethylurea,
3-(2-Hydroxy-4-methylamino-5-methoxyphenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-methylamino-5-methoxyphenyl)-1-isopropylurea,
3-(2-Hydroxy-4-methylamino-5-methoxyphenyl)-1,1-dimethylurea,
3-(2-Hydroxy-4-methylamino-5-methoxyphenyl)-1,1-diethylurea,
3-(2-Hydroxy-4-methylamino-5-methoxyphenyl)-1,1-di(2-hydroxyethyl)urea,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)carbamic acid methyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)carbamic acid isopropyl ester,
1(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)urea,
3(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)-1-methylurea,
3(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)-1-ethylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)-1-isopropylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)-1,1-dimethylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)-1,1-diethylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)-1,1-di(2-hydroxyethyl)urea,
(2-Hydroxy-3-methoxycarbonylaminophenyl)carbamic acid methyl ester,
(2-Hydroxy-3-ethoxycarbonylaminophenyl)carbamic acid ethyl ester,
(2-Hydroxy-3-(2-hydroxyethoxy)carbonylaminophenyl)-carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-3-isopropoxycarbonylaminophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-3-ureidophenyl)urea,
3-(2-Hydroxy-3-(3-methylureido)phenyl)-1-methylurea,
3-(2-Hydroxy-3-(3-ethylureido)phenyl)-1-ethylurea,
3-(2-Hydroxy-3-(3-(2-hydroxyethyl)ureido)phenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-3-(3-isopropylureido)phenyl)-1-isopropylurea,
3-(2-Hydroxy-3-(3,3-dimethylureido)phenyl)-1,1-dimethylurea, and their acid addition salts.
In another embodiment, at least one coupler of formula (I) is chosen from:
(2-Hydroxy-4-aminophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-aminophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-aminophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-aminophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-aminophenyl)urea,
3-(2-Hydroxy-4-aminophenyl)-1-methylurea,
3-(2-Hydroxy-4-aminophenyl)-1-ethylurea,
3-(2-Hydroxy-4-aminophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-aminophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-aminophenyl)-1,1-dimethylurea,
(2-Hydroxy-4-methylaminophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-methylaminophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-methylaminophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-methylaminophenyl)carbamic acid isopropyl ester,
1(2-Hydroxy-4-methylaminophenyl)urea,
3-(2-Hydroxy-4-methylaminophenyl)-1-methylurea,
3-(2-Hydroxy-4-methylaminophenyl)-1-ethylurea,
3-(2-Hydroxy-4-methylaminophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-methylaminophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-methylaminophenyl)-1,1-dimethylurea,
(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)urea,
3-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)-1-methylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)-1-ethylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)aminophenyl)-1,1-dimethylurea,
(2-Hydroxy-4-amino-5-chlorophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-amino-5-chlorophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-amino-5-chlorophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-amino-5-chlorophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-amino-5-chlorophenyl)urea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1-methylurea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1-ethylurea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1,1-dimethylurea,
(2-Hydroxy-4-methylamino-5-chlorophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-methylamino-5-chlorophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-methylamino-5-chlorophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-methylamino-5-chlorophenyl)carbamic acid isopropyl ester,
(2-Hydroxy-4-methylamino-5-chlorophenyl)urea,
3-(2-Hydroxy-4-methylamino-5-chlorophenyl)-1-methylurea,
3-(2-Hydroxy-4-methylamino-5-chlorophenyl)-1-ethylurea,
3-(2-Hydroxy-4-methylamino-5-chlorophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-methylamino-5-chlorophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-methylamino-5-chlorophenyl)-1,1-dimethylurea,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)urea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)-1-methylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)-1-ethylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-chlorophenyl)-1,1-dimethylurea,
(2-Hydroxy-4-amino-5-methoxyphenyl)carbamic acid methyl ester,
(2-Hydroxy-4-amino-5-methoxyphenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-amino-5-methoxyphenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-amino-5-methoxyphenyl)carbamic acid isopropyl ester,
3-(2-Hydroxy-4-amino-5-methoxyphenyl)-1-(2-hydroxyethyl)urea,
(2-Hydroxy-4-methylamino-5-methoxyphenyl)carbamic acid methyl ester,
(2-Hydroxy-4-methylamino-5-methoxyphenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-methylamino-5-methoxyphenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-methylamino-5-methoxyphenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-methylamino-5-methoxyphenyl)urea,
3-(2-Hydroxy-4-methylamino-5-methoxyphenyl)-1-methylurea,
3-(2-Hydroxy-4-methylamino-5-methoxyphenyl)-1-ethylurea,
3-(2-Hydroxy-4-methylamino-5-methoxyphenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-methylamino-5-methoxyphenyl)-1-isopropylurea,
3-(2-Hydroxy-4-methylamino-5-methoxyphenyl)-1,1-dimethylurea,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)carbamic acid methyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-(2-hydroxyethyl)amino-5-ethoxyphenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)urea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)-1-methylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)-1-ethylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)-1-isopropylurea,
3-(2-Hydroxy-4-(2-hydroxyethyl)amino-5-methoxyphenyl)-1,1-dimethylurea, and their acid addition salts.
In another embodiment of the invention, the at least one coupler of formula (I) is chosen from:
(2-Hydroxy-4-aminophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-aminophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-aminophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-aminophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-aminophenyl)urea,
3-(2-Hydroxy-4-aminophenyl)-1-methylurea,
3-(2-Hydroxy-4-aminophenyl)-1-ethylurea,
3-(2-Hydroxy-4-aminophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-aminophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-aminophenyl)-1,1-dimethylurea,
(2-Hydroxy-4-amino-5-chlorophenyl)carbamic acid methyl ester,
(2-Hydroxy-4-amino-5-chlorophenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-amino-5-chlorophenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-amino-5-chlorophenyl)carbamic acid isopropyl ester,
1-(2-Hydroxy-4-amino-5-chlorophenyl)urea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1-methylurea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1-ethylurea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1-(2-hydroxyethyl)urea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1-isopropylurea,
3-(2-Hydroxy-4-amino-5-chlorophenyl)-1,1-dimethylurea,
(2-Hydroxy-4-amino-5-methoxyphenyl)carbamic acid methyl ester,
(2-Hydroxy-4-amino-5-methoxyphenyl)carbamic acid ethyl ester,
(2-Hydroxy-4-amino-5-methoxyphenyl)carbamic acid 2-hydroxyethyl ester,
(2-Hydroxy-4-amino-5-methoxyphenyl)carbamic acid isopropyl ester,
3-(2-Hydroxy-4-amino-5-methoxyphenyl)-1-(2-hydroxyethyl)urea, and their acid addition salts.
The compounds of formula (I) in accordance with the invention are known compounds which may be prepared according to conventional methods well known in the state of the art and which are described, for, example, in patent applications and patents JP 43008269, DE 2 156 480, U.S. Pat. No. 4,310,527, JP 60108844, CS 235432, U.S. Pat. No. 3,767,412, JP 02220047, JP 61035444, JP 60237444, DE 3 524 519, EP 0 086 126, U.S. Pat. No. 2,795,610 or in J. Heterocyclic Chem. 1983, 20, 1423, J. Mol. Struct. 1995, 344, 251, which are incorporated by reference herein.
The at least one coupler of formula (I) in accordance with the invention is present, for example, in an amount ranging from 0.0005 to 12% by weight relative to the total weight of the dyeing composition. In another embodiment, at least one coupler of formula (I) is present, for example, in an amount ranging from 0.005 to 6% by weight relative to the total weight of the dyeing composition.
The nature of the at least one oxidation base which may be used in the dyeing composition in accordance with the invention is not critical. The at least one oxidation base may be chosen from oxidation bases conventionally used in oxidation dyeing, for example, para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Examples of para-phenylenediamines comprise para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-chloroaniline, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(xcex2-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl-xcex2-hydroxyethyl)-para-phenylenediamine, N-(xcex2,xcex3-dihydroxypropyl)-para-phenylenediamine, N-(4xe2x80x2-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-xcex2-hydroxyethyloxy-para-phenylenediamine, 2-xcex2-acetylaminoethyloxy-para-phenylenediamine, N-(xcex2-methoxyethyl)-para-phenylenediamine, and their acid addition salts.
In one embodiment of the invention, the para-phenylenediamines are chosen from para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-xcex2-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine, and 2-xcex2-acetylaminoethyloxy-para-phenylenediamine, and their acid addition salts.
Examples of the bisphenylalkylenediamines may include N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diaminopropanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(ethyl)-N,Nxe2x80x2-bis(4xe2x80x2-amino-3xe2x80x2-methylphenyl)ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their acid addition salts.
Examples of the para-aminophenols may include para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(xcex2-hydroxyethylaminomethyl)phenol, 4-amino-2-fluorophenol, and their acid addition salts.
Examples of the ortho-aminophenols may include 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol, and their acid addition salts.
Examples of the heterocyclic bases may include pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
Examples of the pyridine derivatives may include the compounds described, for example, in Patents GB 1,026,978 and GB 1,153,196, incorporated by reference herein, such as
2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(xcex2-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine, and their acid addition salts.
Examples of the pyrimidine derivatives may include compounds described in German Patent DE 2,359,399, Japanese Patents JP 88-169,571 and JP 91-10659, and Patent Application WO 96/15765, incorporated by reference herein, such as
2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine; and the pyrazolopyrimidine derivatives such as those mentioned in Patent Application FR-A-2,750,048, incorporated by reference herein, and among which may include pyrazolo[1,5-a]pyrimidine-3,7-diamine, 2-methylpyrazolo[1,5-a]pyrimidine-3,7-diamine; 5-methylpyrazolo[1,5-a]pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine; 3-aminopyrazolo[1,5-a]pyrimidin-7-ol; 3-aminopyrazolo[1,5-a]pyrimidin-5-ol; 2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)amino]ethanol, 2-[(7-aminopyrazolo[1,5-a]-pyrimidin-3-yl)-(2-hydroxyethyl)amino]ethanol, 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]pyrimidine, their tautomeric forms, when a tautomeric equilibrium exists and their acid addition salts.
Examples of pyrazole derivatives may include the compounds described in Patents DE 3,843,892, DE 4,133,957, and Patent Applications WO 94/08969, WO 94/08970, FR-A-2,733,749 and DE 195 43 988, incorporated by reference herein, such as
4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-l-(4xe2x80x2-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(xcex2-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4xe2x80x2-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2xe2x80x2-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4-(xcex2-hydroxyethyl)amino-1-methylpyrazole, and their acid addition salts.
In one embodiment of the invention, the at least one oxidation base can be present in an amount ranging, for example, from 0.0005 to 12% by weight relative to the total weight of the dyeing composition. In another embodiment, the at least one oxidation base can be present in an amount ranging, for example, from 0.005 to 6% by weight relative to the total weight of the dyeing composition.
The dyeing composition in accordance with the invention may also contain, in addition to the at least one coupler chosen from formula (I) above, at least one additional coupler which may be chosen from couplers conventionally used in oxidation dyeing, for example, meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers such as, indole derivatives, indoline derivatives, pyridine derivatives and pyrazolones, and their acid addition salts.
In one embodiment of the invention, the at least one additional coupler is chosen from
2-methyl-5-aminophenol, 5-N-(xcex2-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(xcex2-hydroxyethyloxy)benzene, 2-amino-4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, xcex1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, and their acid addition salts.
When present, the at least one additional coupler is present in an amount ranging, for example, from 0.0001 to 10% by weight relative to the total weight of the dyeing composition. In another embodiment of the invention, the at least one additional coupler is present in an amount ranging, for example, from 0.005 to 5% by weight relative to the total weight of the dyeing composition.
In general, the acid addition salts which can be used in the context of the dyeing compositions of the invention (compounds of formula (I), oxidation bases and additional couplers) may be chosen from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, and acetates.
The medium suitable for dyeing (or carrier) generally comprises water, and a mixture of water and at least one organic solvent for solubilizing the compounds which might not be sufficiently soluble in water. Examples of the at least one organic solvent may include C1-C4 alkanols such as ethanol and isopropanol, glycerol, glycols, and glycol ethers, such as 2-butoxyethanol, propylene glycol, monomethyl ether of propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol, as well as, aromatic alcohols such as benzyl alcohol and phenoxyethanol, and similar products.
The at least one organic solvent may be present in an amount ranging, for example, from 1 to 40% by weight relative to the total weight of the dyeing composition. In another embodiment, the at least one organic solvent may be present in a amount ranging, for example, from 5 to 30% by weight relative to the total weight of the dyeing composition.
In one embodiment of the invention, the pH of the dyeing composition ranges, for example, from 3 to 12. In another embodiment, the pH ranges, for example, from 5 to 11. The pH may be adjusted to the desired value by means of acidifying or alkalinizing agents normally used in dyeing keratinous fibers.
Examples of acidifying agents may include inorganic and organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid and sulphonic acids.
Examples of alkalinizing agents may include aqueous ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and the compounds of the following formula (II): 
wherein:
W is a propylene residue, optionally substituted with a group chosen from a hydroxyl group and a C1-C6 alkyl group, R20, R21, R22 and R23, which are identical or different, are each chosen from a hydrogen atom, and C1-C6 alkyl and C1-C6 hydroxyalkyl groups.
The oxidation dyeing compositions in accordance with the invention may also contain at least one direct dye, which may be helpful in modifying the shades and enriching them with glints.
In one embodiment, the dyeing composition in accordance with the invention, may also contain various adjuvants conventionally used in hair-dyeing compositions, such as, anionic, cationic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof, anionic, cationic, nonionic, amphoteric and zwitterionic polymers and mixtures thereof, inorganic and organic thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents, for example, modified or unmodified, volatile and nonvolatile, silicones, film-forming agents, ceramides, preservatives, and opacifying agents.
Of course persons skilled in the art may choose these possible additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition in accordance with the invention are not substantially impaired by the additions envisaged.
The dyeing composition according to the invention may be provided in various forms, such as, liquids, creams, gels, or in any other form suitable for dyeing keratinous fibers, such as human hair.
One embodiment of the invention is the use of the compounds of formula (I) as defined above as a coupler for the oxidation dyeing of keratinous fibers, for example, human keratinous fibers such as hair.
Another embodiment of the invention is a method of oxidation dyeing keratinous fibers, for example, human keratinous fibers such as hair, using the dyeing composition as defined above.
According to this method, at least one dyeing composition, as defined above, is applied to the fibers, the color being developed at acidic, neutral or alkaline pH with the aid of an oxidizing agent which (1) may be added just at the time of use to the dyeing composition, or (2) may be present in an oxidizing composition applied simultaneously or sequentially.
In one embodiment of the dyeing method, the dyeing composition described above may be mixed, at the time of use, with an oxidizing composition comprising, in a medium suitable for dyeing, at least one oxidizing agent present in a sufficient quantity to develop a color. The mixture obtained may then be applied to the keratinous fibers and allowed to act for 3 to 50 minutes after which they may be rinsed, washed with shampoo, rinsed again and dried.
In another embodiment, the dyeing composition described above may be mixed, at the time of use, with an oxidizing composition comprising, in a medium suitable for dyeing, at least one oxidizing agent present in a sufficient quantity to develop a color. The mixture obtained may then be applied to the keratinous fibers and allowed to act for 5 to 30 minutes after which they may be rinsed, washed with shampoo, rinsed again and dried.
The oxidizing agent may be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratinous fibers, such as hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, such as perborates and persulphates, peracids, and enzymes such as peroxidases, laccases, tyrosinases and oxidoreductases. Examples of the enzymes may include pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases and uricases.
The pH of the oxidizing composition containing the oxidizing agent as defined above may be such that after mixing with the dyeing composition, the pH of the resulting composition applied to the keratinous fibers ranges, for example, from 3 to 12. In another embodiment of the invention, the pH of the resulting composition applied to the keratinous fibers ranges, for example, from 5 to 11. The pH may be adjusted to the desired value by means of acidifying and alkalinizing agents normally used in dyeing keratinous fibers and as defined above.
The oxidizing composition as defined above may also comprise various adjuvants conventionally used in hair-dyeing compositions and as defined above.
The composition finally applied to the keratinous fibers, may be provided in various forms, such as liquids, creams, gels, and any other form suitable for dyeing keratinous fibers, such as human hair.
Another embodiment of the invention is chosen from a multicompartment device, dyeing xe2x80x9ckitxe2x80x9d and any other multicompartment packaging system wherein a first compartment comprises the dyeing composition as defined above and a second compartment comprises the oxidizing composition as defined above. These devices may be equipped with a means to deliver the desired mixture to the hair, such as the devices described in Patent FR-2,586,913, which is incorporated by reference herein.
Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term xe2x80x9caboutxe2x80x9d. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
The following examples are intended to illustrate the invention without in anyway limiting the scope thereof.